Organic materials for organic light emitting devices

ABSTRACT

Novel diarylamino phenyl carbazole compounds are provided. By appropriately selecting the nature of the diarylamino substituent and the substitution on the carbazole nitrogen, compounds with appropriate HOMO and LUMO energies can be obtained for use as materials in a secondary hole transport layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patent application Ser. No. 13/421,489, filed Mar. 15, 2012, the disclosure of which is expressly incorporated herein by reference in its entirety.

JOINT RESEARCH AGREEMENTS

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: Regents of the University of Michigan, Princeton University, University of Southern California, and Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to novel diarylamino phenyl carbazole compounds. In particular, these compounds are useful as materials that can be incorporated into a secondary hole transport layer in OLED devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY OF THE INVENTION

In one aspect, a compound having the formula I is provided:

In the compound of Formula I, Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, R₃ and R₄ are independently selected from the group consisting of alkyl, heteroalkyl, arylalkyl, aryl, and heteroaryl. In one aspect, R₃ and R₄ are hydrogen or deuterium.

In one aspect, the compound has the formula:

In one aspect, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one aspect, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one aspect, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one aspect, X is O or S. In one aspect, Ar₁ and Ar₂ are aryl.

In one aspect, the compound is selected from the group consisting of:

In one aspect, a first device is provided. The first device comprises an organic light emitting device, further comprising: an anode, a cathode, a hole injection layer disposed between the anode and the emissive layer, a first hole transport layer disposed between the hole injection layer and the emissive layer, and a second hole transport layer disposed between the first hole transport layer and the emissive layer, and wherein the second hole transport layer comprises a compound of formula:

In the compound of Formula II, Ar₁, Ar₂, and Ar₅ are independently selected from the group consisting of aryl and heteroaryl and R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the compound has the formula:

wherein X is selected from the group consisting of O, S, and Se, wherein R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the second hole transport layer is disposed adjacent to the first hole transport layer. In one aspect, the first hole transport layer is thicker than the second hole transport layer. In one aspect, the first hole transport layer comprises a compound with the formula:

wherein Ar_(a), Ar_(b), Ar_(c) and Ar_(d) are independently selected from the group consisting of aryl and heteroaryl.

In one aspect, the triplet energy of the compound of Formula II is higher than the emission energy of the emissive layer.

In one aspect, Ar₁, Ar₂ and Ar₅ are independently selected from the group consisting of:

In one aspect, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one aspect, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one aspect, the first device further comprises a first dopant material that is an emissive dopant comprising a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein R_(a), R_(b), R_(c), and R_(d) may represent mono, di, tri, or tetra substitution, or no substitution and wherein R_(a), R_(b), R_(c), and R_(d) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) are optionally joined to form a fused ring or form a multidentate ligand.

In one aspect, the first device is a consumer product. In one aspect, the first device is an organic light-emitting device. In one aspect, the first device comprises a lighting panel. In one aspect, a first device comprising an organic light emitting device, further comprising an anode, a cathode, a first organic layer disposed between the anode and the cathode, and wherein the first organic layer comprises a compound of formula:

In the compound of Formula I, Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the first organic layer is an emissive layer. In one aspect, the emissive layer is a phosphorescent emissive layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIG. 3 shows a compound of Formula I.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. patent application Ser. No. 10/233,470, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention may be incorporated into a wide variety of consumer products, including flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads up displays, fully transparent displays, flexible displays, laser printers, telephones, cell phones, personal digital assistants (PDAs), laptop computers, digital cameras, camcorders, viewfinders, micro-displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.).

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The terms halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, arylkyl, heterocyclic group, aryl, aromatic group, and heteroaryl are known to the art, and are defined in U.S. Pat. No. 7,279,704 at cols. 31-32, which are incorporated herein by reference.

In one embodiment, a compound having the formula I is provided:

In the compound of Formula I, Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, R₃ and R₄ are independently selected from the group consisting of alkyl, heteroalkyl, arylalkyl, aryl, and heteroaryl. In one embodiment, R₃ and R₄ are hydrogen or deuterium.

In one embodiment, the compound has the formula:

In one embodiment, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one embodiment, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one embodiment, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one embodiment, X is O or S. In one embodiment, Ar₁ and Ar₂ are aryl.

In one embodiment, the compound is selected from the group consisting of:

In some embodiments, the compounds are selected from the group consisting of Compound 1-Compound 1183 as depicted in Table 1. The list of substituents in Table 1 is as follows:

The subscript “x” in Ar_(x) depends on whether the group is Ar₁, Ar₂, or Ar₅.

Ar₅ Ar₅- Ar₅- Ar₅- Ar₅- Ar₁ Ar₂ Ar₅-1 Ar₅-2 Ar₅-3 Ar₅-4 Ar₅-5 Ar₅-6 Ar₅-7 Ar₅-8 Ar₅-9 10 11 12 13 Compound Ar₁-1 Ar₂-1 x 1 Ar₁-1 Ar₂-1 x 2 Ar₁-1 Ar₂-1 x 3 Ar₁-1 Ar₂-1 x 4 Ar₁-1 Ar₂-1 x 5 Ar₁-1 Ar₂-1 x 6 Ar₁-1 Ar₂-1 x 7 Ar₁-1 Ar₂-1 x 8 Ar₁-1 Ar₂-1 x 9 Ar₁-1 Ar₂-1 x 10 Ar₁-1 Ar₂-1 x 11 Ar₁-1 Ar₂-1 x 12 Ar₁-1 Ar₂-1 x 13 Ar₁-1 Ar₂-2 x 14 Ar₁-1 Ar₂-2 x 15 Ar₁-1 Ar₂-2 x 16 Ar₁-1 Ar₂-2 x 17 Ar₁-1 Ar₂-2 x 18 Ar₁-1 Ar₂-2 x 19 Ar₁-1 Ar₂-2 x 20 Ar₁-1 Ar₂-2 x 21 Ar₁-1 Ar₂-2 x 22 Ar₁-1 Ar₂-2 x 23 Ar₁-1 Ar₂-2 x 24 Ar₁-1 Ar₂-2 x 25 Ar₁-1 Ar₂-2 x 26 Ar₁-1 Ar₂-3 x 27 Ar₁-1 Ar₂-3 x 28 Ar₁-1 Ar₂-3 x 29 Ar₁-1 Ar₂-3 x 30 Ar₁-1 Ar₂-3 x 31 Ar₁-1 Ar₂-3 x 32 Ar₁-1 Ar₂-3 x 33 Ar₁-1 Ar₂-3 x 34 Ar₁-1 Ar₂-3 x 35 Ar₁-1 Ar₂-3 x 36 Ar₁-1 Ar₂-3 x 37 Ar₁-1 Ar₂-3 x 38 Ar₁-1 Ar₂-3 x 39 Ar₁-1 Ar₂-4 x 40 Ar₁-1 Ar₂-4 x 41 Ar₁-1 Ar₂-4 x 42 Ar₁-1 Ar₂-4 x 43 Ar₁-1 Ar₂-4 x 44 Ar₁-1 Ar₂-4 x 45 Ar₁-1 Ar₂-4 x 46 Ar₁-1 Ar₂-4 x 47 Ar₁-1 Ar₂-4 x 48 Ar₁-1 Ar₂-4 x 49 Ar₁-1 Ar₂-4 x 50 Ar₁-1 Ar₂-4 x 51 Ar₁-1 Ar₂-4 x 52 Ar₁-1 Ar₂-5 x 53 Ar₁-1 Ar₂-5 x 54 Ar₁-1 Ar₂-5 x 55 Ar₁-1 Ar₂-5 x 56 Ar₁-1 Ar₂-5 x 57 Ar₁-1 Ar₂-5 x 58 Ar₁-1 Ar₂-5 x 59 Ar₁-1 Ar₂-5 x 60 Ar₁-1 Ar₂-5 x 61 Ar₁-1 Ar₂-5 x 62 Ar₁-1 Ar₂-5 x 63 Ar₁-1 Ar₂-5 x 64 Ar₁-1 Ar₂-5 x 65 Ar₁-1 Ar₂-6 x 66 Ar₁-1 Ar₂-6 x 67 Ar₁-1 Ar₂-6 x 68 Ar₁-1 Ar₂-6 x 69 Ar₁-1 Ar₂-6 x 70 Ar₁-1 Ar₂-6 x 71 Ar₁-1 Ar₂-6 x 72 Ar₁-1 Ar₂-6 x 73 Ar₁-1 Ar₂-6 x 74 Ar₁-1 Ar₂-6 x 75 Ar₁-1 Ar₂-6 x 76 Ar₁-1 Ar₂-6 x 77 Ar₁-1 Ar₂-6 x 78 Ar₁-1 Ar₂-7 x 79 Ar₁-1 Ar₂-7 x 80 Ar₁-1 Ar₂-7 x 81 Ar₁-1 Ar₂-7 x 82 Ar₁-1 Ar₂-7 x 83 Ar₁-1 Ar₂-7 x 84 Ar₁-1 Ar₂-7 x 85 Ar₁-1 Ar₂-7 x 86 Ar₁-1 Ar₂-7 x 87 Ar₁-1 Ar₂-7 x 88 Ar₁-1 Ar₂-7 x 89 Ar₁-1 Ar₂-7 x 90 Ar₁-1 Ar₂-7 x 91 Ar₁-1 Ar₂-8 x 92 Ar₁-1 Ar₂-8 x 93 Ar₁-1 Ar₂-8 x 94 Ar₁-1 Ar₂-8 x 95 Ar₁-1 Ar₂-8 x 96 Ar₁-1 Ar₂-8 x 97 Ar₁-1 Ar₂-8 x 98 Ar₁-1 Ar₂-8 x 99 Ar₁-1 Ar₂-8 x 100 Ar₁-1 Ar₂-8 x 101 Ar₁-1 Ar₂-8 x 102 Ar₁-1 Ar₂-8 x 103 Ar₁-1 Ar₂-8 x 104 Ar₁-1 Ar₂-9 x 105 Ar₁-1 Ar₂-9 x 106 Ar₁-1 Ar₂-9 x 107 Ar₁-1 Ar₂-9 x 108 Ar₁-1 Ar₂-9 x 109 Ar₁-1 Ar₂-9 x 110 Ar₁-1 Ar₂-9 x 111 Ar₁-1 Ar₂-9 x 112 Ar₁-1 Ar₂-9 x 113 Ar₁-1 Ar₂-9 x 114 Ar₁-1 Ar₂-9 x 115 Ar₁-1 Ar₂-9 x 116 Ar₁-1 Ar₂-9 x 117 Ar₁-1 Ar₂- x 118 10 Ar₁-1 Ar₂- x 119 10 Ar₁-1 Ar₂- x 120 10 Ar₁-1 Ar₂- x 121 10 Ar₁-1 Ar₂- x 122 10 Ar₁-1 Ar₂- x 123 10 Ar₁-1 Ar₂- x 124 10 Ar₁-1 Ar₂- x 125 10 Ar₁-1 Ar₂- x 126 10 Ar₁-1 Ar₂- x 127 10 Ar₁-1 Ar₂- x 128 10 Ar₁-1 Ar₂- x 129 10 Ar₁-1 Ar₂- x 130 10 Ar₁-1 Ar₂- x 131 11 Ar₁-1 Ar₂- x 132 11 Ar₁-1 Ar₂- x 133 11 Ar₁-1 Ar₂- x 134 11 Ar₁-1 Ar₂- x 135 11 Ar₁-1 Ar₂- x 136 11 Ar₁-1 Ar₂- x 137 11 Ar₁-1 Ar₂- x 138 11 Ar₁-1 Ar₂- x 139 11 Ar₁-1 Ar₂- x 140 11 Ar₁-1 Ar₂- x 141 11 Ar₁-1 Ar₂- x 142 11 Ar₁-1 Ar₂- x 143 11 Ar₁-1 Ar₂- x 144 12 Ar₁-1 Ar₂- x 145 12 Ar₁-1 Ar₂- x 146 12 Ar₁-1 Ar₂- x 147 12 Ar₁-1 Ar₂- x 148 12 Ar₁-1 Ar₂- x 149 12 Ar₁-1 Ar₂- x 150 12 Ar₁-1 Ar₂- x 151 12 Ar₁-1 Ar₂- x 152 12 Ar₁-1 Ar₂- x 153 12 Ar₁-1 Ar₂- x 154 12 Ar₁-1 Ar₂- x 155 12 Ar₁-1 Ar₂- x 156 12 Ar₁-1 Ar₂- x 157 13 Ar₁-1 Ar₂- x 158 13 Ar₁-1 Ar₂- x 159 13 Ar₁-1 Ar₂- x 160 13 Ar₁-1 Ar₂- x 161 13 Ar₁-1 Ar₂- x 162 13 Ar₁-1 Ar₂- x 163 13 Ar₁-1 Ar₂- x 164 13 Ar₁-1 Ar₂- x 165 13 Ar₁-1 Ar₂- x 166 13 Ar₁-1 Ar₂- x 167 13 Ar₁-1 Ar₂- x 168 13 Ar₁-1 Ar₂- x 169 13 Ar₁-2 Ar₂-2 x 170 Ar₁-2 Ar₂-2 x 171 Ar₁-2 Ar₂-2 x 172 Ar₁-2 Ar₂-2 x 173 Ar₁-2 Ar₂-2 x 174 Ar₁-2 Ar₂-2 x 175 Ar₁-2 Ar₂-2 x 176 Ar₁-2 Ar₂-2 x 177 Ar₁-2 Ar₂-2 x 178 Ar₁-2 Ar₂-2 x 179 Ar₁-2 Ar₂-2 x 180 Ar₁-2 Ar₂-2 x 181 Ar₁-2 Ar₂-2 x 182 Ar₁-2 Ar₂-3 x 183 Ar₁-2 Ar₂-3 x 184 Ar₁-2 Ar₂-3 x 185 Ar₁-2 Ar₂-3 x 186 Ar₁-2 Ar₂-3 x 187 Ar₁-2 Ar₂-3 x 188 Ar₁-2 Ar₂-3 x 189 Ar₁-2 Ar₂-3 x 190 Ar₁-2 Ar₂-3 x 191 Ar₁-2 Ar₂-3 x 192 Ar₁-2 Ar₂-3 x 193 Ar₁-2 Ar₂-3 x 194 Ar₁-2 Ar₂-3 x 195 Ar₁-2 Ar₂-4 x 196 Ar₁-2 Ar₂-4 x 197 Ar₁-2 Ar₂-4 x 198 Ar₁-2 Ar₂-4 x 199 Ar₁-2 Ar₂-4 x 200 Ar₁-2 Ar₂-4 x 201 Ar₁-2 Ar₂-4 x 202 Ar₁-2 Ar₂-4 x 203 Ar₁-2 Ar₂-4 x 204 Ar₁-2 Ar₂-4 x 205 Ar₁-2 Ar₂-4 x 206 Ar₁-2 Ar₂-4 x 207 Ar₁-2 Ar₂-4 x 208 Ar₁-2 Ar₂-5 x 209 Ar₁-2 Ar₂-5 x 210 Ar₁-2 Ar₂-5 x 211 Ar₁-2 Ar₂-5 x 212 Ar₁-2 Ar₂-5 x 213 Ar₁-2 Ar₂-5 x 214 Ar₁-2 Ar₂-5 x 215 Ar₁-2 Ar₂-5 x 216 Ar₁-2 Ar₂-5 x 217 Ar₁-2 Ar₂-5 x 218 Ar₁-2 Ar₂-5 x 219 Ar₁-2 Ar₂-5 x 220 Ar₁-2 Ar₂-5 x 221 Ar₁-2 Ar₂-6 x 222 Ar₁-2 Ar₂-6 x 223 Ar₁-2 Ar₂-6 x 224 Ar₁-2 Ar₂-6 x 225 Ar₁-2 Ar₂-6 x 226 Ar₁-2 Ar₂-6 x 227 Ar₁-2 Ar₂-6 x 228 Ar₁-2 Ar₂-6 x 229 Ar₁-2 Ar₂-6 x 230 Ar₁-2 Ar₂-6 x 231 Ar₁-2 Ar₂-6 x 232 Ar₁-2 Ar₂-6 x 233 Ar₁-2 Ar₂-6 x 234 Ar₁-2 Ar₂-7 x 235 Ar₁-2 Ar₂-7 x 236 Ar₁-2 Ar₂-7 x 237 Ar₁-2 Ar₂-7 x 238 Ar₁-2 Ar₂-7 x 239 Ar₁-2 Ar₂-7 x 240 Ar₁-2 Ar₂-7 x 241 Ar₁-2 Ar₂-7 x 242 Ar₁-2 Ar₂-7 x 243 Ar₁-2 Ar₂-7 x 244 Ar₁-2 Ar₂-7 x 245 Ar₁-2 Ar₂-7 x 246 Ar₁-2 Ar₂-7 x 247 Ar₁-2 Ar₂-8 x 248 Ar₁-2 Ar₂-8 x 249 Ar₁-2 Ar₂-8 x 250 Ar₁-2 Ar₂-8 x 251 Ar₁-2 Ar₂-8 x 252 Ar₁-2 Ar₂-8 x 253 Ar₁-2 Ar₂-8 x 254 Ar₁-2 Ar₂-8 x 255 Ar₁-2 Ar₂-8 x 256 Ar₁-2 Ar₂-8 x 257 Ar₁-2 Ar₂-8 x 258 Ar₁-2 Ar₂-8 x 259 Ar₁-2 Ar₂-8 x 260 Ar₁-2 Ar₂-9 x 261 Ar₁-2 Ar₂-9 x 262 Ar₁-2 Ar₂-9 x 263 Ar₁-2 Ar₂-9 x 264 Ar₁-2 Ar₂-9 x 265 Ar₁-2 Ar₂-9 x 266 Ar₁-2 Ar₂-9 x 267 Ar₁-2 Ar₂-9 x 268 Ar₁-2 Ar₂-9 x 269 Ar₁-2 Ar₂-9 x 270 Ar₁-2 Ar₂-9 x 271 Ar₁-2 Ar₂-9 x 272 Ar₁-2 Ar₂-9 x 273 Ar₁-2 Ar₂- x 274 10 Ar₁-2 Ar₂- x 275 10 Ar₁-2 Ar₂- x 276 10 Ar₁-2 Ar₂- x 277 10 Ar₁-2 Ar₂- x 278 10 Ar₁-2 Ar₂- x 279 10 Ar₁-2 Ar₂- x 280 10 Ar₁-2 Ar₂- x 281 10 Ar₁-2 Ar₂- x 282 10 Ar₁-2 Ar₂- x 283 10 Ar₁-2 Ar₂- x 284 10 Ar₁-2 Ar₂- x 285 10 Ar₁-2 Ar₂- x 286 10 Ar₁-2 Ar₂- x 287 11 Ar₁-2 Ar₂- x 288 11 Ar₁-2 Ar₂- x 289 11 Ar₁-2 Ar₂- x 290 11 Ar₁-2 Ar₂- x 291 11 Ar₁-2 Ar₂- x 292 11 Ar₁-2 Ar₂- x 293 11 Ar₁-2 Ar₂- x 294 11 Ar₁-2 Ar₂- x 295 11 Ar₁-2 Ar₂- x 296 11 Ar₁-2 Ar₂- x 297 11 Ar₁-2 Ar₂- x 298 11 Ar₁-2 Ar₂- x 299 11 Ar₁-2 Ar₂- x 300 12 Ar₁-2 Ar₂- x 301 12 Ar₁-2 Ar₂- x 302 12 Ar₁-2 Ar₂- x 303 12 Ar₁-2 Ar₂- x 304 12 Ar₁-2 Ar₂- x 305 12 Ar₁-2 Ar₂- x 306 12 Ar₁-2 Ar₂- x 307 12 Ar₁-2 Ar₂- x 308 12 Ar₁-2 Ar₂- x 309 12 Ar₁-2 Ar₂- x 310 12 Ar₁-2 Ar₂- x 311 12 Ar₁-2 Ar₂- x 312 12 Ar₁-2 Ar₂- x 313 13 Ar₁-2 Ar₂- x 314 13 Ar₁-2 Ar₂- x 315 13 Ar₁-2 Ar₂- x 316 13 Ar₁-2 Ar₂- x 317 13 Ar₁-2 Ar₂- x 318 13 Ar₁-2 Ar₂- x 319 13 Ar₁-2 Ar₂- x 320 13 Ar₁-2 Ar₂- x 321 13 Ar₁-2 Ar₂- x 322 13 Ar₁-2 Ar₂- x 323 13 Ar₁-2 Ar₂- x 324 13 Ar₁-2 Ar₂- x 325 13 Ar₁-3 Ar₂-3 x 326 Ar₁-3 Ar₂-3 x 327 Ar₁-3 Ar₂-3 x 328 Ar₁-3 Ar₂-3 x 329 Ar₁-3 Ar₂-3 x 330 Ar₁-3 Ar₂-3 x 331 Ar₁-3 Ar₂-3 x 332 Ar₁-3 Ar₂-3 x 333 Ar₁-3 Ar₂-3 x 334 Ar₁-3 Ar₂-3 x 335 Ar₁-3 Ar₂-3 x 336 Ar₁-3 Ar₂-3 x 337 Ar₁-3 Ar₂-3 x 338 Ar₁-3 Ar₂-4 x 339 Ar₁-3 Ar₂-4 x 340 Ar₁-3 Ar₂-4 x 341 Ar₁-3 Ar₂-4 x 342 Ar₁-3 Ar₂-4 x 343 Ar₁-3 Ar₂-4 x 344 Ar₁-3 Ar₂-4 x 345 Ar₁-3 Ar₂-4 x 346 Ar₁-3 Ar₂-4 x 347 Ar₁-3 Ar₂-4 x 348 Ar₁-3 Ar₂-4 x 349 Ar₁-3 Ar₂-4 x 350 Ar₁-3 Ar₂-4 x 351 Ar₁-3 Ar₂-5 x 352 Ar₁-3 Ar₂-5 x 353 Ar₁-3 Ar₂-5 x 354 Ar₁-3 Ar₂-5 x 355 Ar₁-3 Ar₂-5 x 356 Ar₁-3 Ar₂-5 x 357 Ar₁-3 Ar₂-5 x 358 Ar₁-3 Ar₂-5 x 359 Ar₁-3 Ar₂-5 x 360 Ar₁-3 Ar₂-5 x 361 Ar₁-3 Ar₂-5 x 362 Ar₁-3 Ar₂-5 x 363 Ar₁-3 Ar₂-5 x 364 Ar₁-3 Ar₂-6 x 365 Ar₁-3 Ar₂-6 x 366 Ar₁-3 Ar₂-6 x 367 Ar₁-3 Ar₂-6 x 368 Ar₁-3 Ar₂-6 x 369 Ar₁-3 Ar₂-6 x 370 Ar₁-3 Ar₂-6 x 371 Ar₁-3 Ar₂-6 x 372 Ar₁-3 Ar₂-6 x 373 Ar₁-3 Ar₂-6 x 374 Ar₁-3 Ar₂-6 x 375 Ar₁-3 Ar₂-6 x 376 Ar₁-3 Ar₂-6 x 377 Ar₁-3 Ar₂-7 x 378 Ar₁-3 Ar₂-7 x 379 Ar₁-3 Ar₂-7 x 380 Ar₁-3 Ar₂-7 x 381 Ar₁-3 Ar₂-7 x 382 Ar₁-3 Ar₂-7 x 383 Ar₁-3 Ar₂-7 x 384 Ar₁-3 Ar₂-7 x 385 Ar₁-3 Ar₂-7 x 386 Ar₁-3 Ar₂-7 x 387 Ar₁-3 Ar₂-7 x 388 Ar₁-3 Ar₂-7 x 389 Ar₁-3 Ar₂-7 x 390 Ar₁-3 Ar₂-8 x 391 Ar₁-3 Ar₂-8 x 392 Ar₁-3 Ar₂-8 x 393 Ar₁-3 Ar₂-8 x 394 Ar₁-3 Ar₂-8 x 395 Ar₁-3 Ar₂-8 x 396 Ar₁-3 Ar₂-8 x 397 Ar₁-3 Ar₂-8 x 398 Ar₁-3 Ar₂-8 x 399 Ar₁-3 Ar₂-8 x 400 Ar₁-3 Ar₂-8 x 401 Ar₁-3 Ar₂-8 x 402 Ar₁-3 Ar₂-8 x 403 Ar₁-3 Ar₂-9 x 404 Ar₁-3 Ar₂-9 x 405 Ar₁-3 Ar₂-9 x 406 Ar₁-3 Ar₂-9 x 407 Ar₁-3 Ar₂-9 x 408 Ar₁-3 Ar₂-9 x 409 Ar₁-3 Ar₂-9 x 410 Ar₁-3 Ar₂-9 x 411 Ar₁-3 Ar₂-9 x 412 Ar₁-3 Ar₂-9 x 413 Ar₁-3 Ar₂-9 x 414 Ar₁-3 Ar₂-9 x 415 Ar₁-3 Ar₂-9 x 416 Ar₁-3 Ar₂- x 417 10 Ar₁-3 Ar₂- x 418 10 Ar₁-3 Ar₂- x 419 10 Ar₁-3 Ar₂- x 420 10 Ar₁-3 Ar₂- x 421 10 Ar₁-3 Ar₂- x 422 10 Ar₁-3 Ar₂- x 423 10 Ar₁-3 Ar₂- x 424 10 Ar₁-3 Ar₂- x 425 10 Ar₁-3 Ar₂- x 426 10 Ar₁-3 Ar₂- x 427 10 Ar₁-3 Ar₂- x 428 10 Ar₁-3 Ar₂- x 429 10 Ar₁-3 Ar₂- x 430 11 Ar₁-3 Ar₂- x 431 11 Ar₁-3 Ar₂- x 432 11 Ar₁-3 Ar₂- x 433 11 Ar₁-3 Ar₂- x 434 11 Ar₁-3 Ar₂- x 435 11 Ar₁-3 Ar₂- x 436 11 Ar₁-3 Ar₂- x 437 11 Ar₁-3 Ar₂- x 438 11 Ar₁-3 Ar₂- x 439 11 Ar₁-3 Ar₂- x 440 11 Ar₁-3 Ar₂- x 441 11 Ar₁-3 Ar₂- x 442 11 Ar₁-3 Ar₂- x 443 12 Ar₁-3 Ar₂- x 444 12 Ar₁-3 Ar₂- x 445 12 Ar₁-3 Ar₂- x 446 12 Ar₁-3 Ar₂- x 447 12 Ar₁-3 Ar₂- x 448 12 Ar₁-3 Ar₂- x 449 12 Ar₁-3 Ar₂- x 450 12 Ar₁-3 Ar₂- x 451 12 Ar₁-3 Ar₂- x 452 12 Ar₁-3 Ar₂- x 453 12 Ar₁-3 Ar₂- x 454 12 Ar₁-3 Ar₂- x 455 12 Ar₁-3 Ar₂- x 456 13 Ar₁-3 Ar₂- x 457 13 Ar₁-3 Ar₂- x 458 13 Ar₁-3 Ar₂- x 459 13 Ar₁-3 Ar₂- x 460 13 Ar₁-3 Ar₂- x 461 13 Ar₁-3 Ar₂- x 462 13 Ar₁-3 Ar₂- x 463 13 Ar₁-3 Ar₂- x 464 13 Ar₁-3 Ar₂- x 465 13 Ar₁-3 Ar₂- x 466 13 Ar₁-3 Ar₂- x 467 13 Ar₁-3 Ar₂- x 468 13 Ar₁-4 Ar₂-4 x 469 Ar₁-4 Ar₂-4 x 470 Ar₁-4 Ar₂-4 x 471 Ar₁-4 Ar₂-4 x 472 Ar₁-4 Ar₂-4 x 473 Ar₁-4 Ar₂-4 x 474 Ar₁-4 Ar₂-4 x 475 Ar₁-4 Ar₂-4 x 476 Ar₁-4 Ar₂-4 x 477 Ar₁-4 Ar₂-4 x 478 Ar₁-4 Ar₂-4 x 479 Ar₁-4 Ar₂-4 x 480 Ar₁-4 Ar₂-4 x 481 Ar₁-4 Ar₂-5 x 482 Ar₁-4 Ar₂-5 x 483 Ar₁-4 Ar₂-5 x 484 Ar₁-4 Ar₂-5 x 485 Ar₁-4 Ar₂-5 x 486 Ar₁-4 Ar₂-5 x 487 Ar₁-4 Ar₂-5 x 488 Ar₁-4 Ar₂-5 x 489 Ar₁-4 Ar₂-5 x 490 Ar₁-4 Ar₂-5 x 491 Ar₁-4 Ar₂-5 x 492 Ar₁-4 Ar₂-5 x 493 Ar₁-4 Ar₂-5 x 494 Ar₁-4 Ar₂-6 x 495 Ar₁-4 Ar₂-6 x 496 Ar₁-4 Ar₂-6 x 497 Ar₁-4 Ar₂-6 x 498 Ar₁-4 Ar₂-6 x 499 Ar₁-4 Ar₂-6 x 500 Ar₁-4 Ar₂-6 x 501 Ar₁-4 Ar₂-6 x 502 Ar₁-4 Ar₂-6 x 503 Ar₁-4 Ar₂-6 x 504 Ar₁-4 Ar₂-6 x 505 Ar₁-4 Ar₂-6 x 506 Ar₁-4 Ar₂-6 x 507 Ar₁-4 Ar₂-7 x 508 Ar₁-4 Ar₂-7 x 509 Ar₁-4 Ar₂-7 x 510 Ar₁-4 Ar₂-7 x 511 Ar₁-4 Ar₂-7 x 512 Ar₁-4 Ar₂-7 x 513 Ar₁-4 Ar₂-7 x 514 Ar₁-4 Ar₂-7 x 515 Ar₁-4 Ar₂-7 x 516 Ar₁-4 Ar₂-7 x 517 Ar₁-4 Ar₂-7 x 518 Ar₁-4 Ar₂-7 x 519 Ar₁-4 Ar₂-7 x 520 Ar₁-4 Ar₂-8 x 521 Ar₁-4 Ar₂-8 x 522 Ar₁-4 Ar₂-8 x 523 Ar₁-4 Ar₂-8 x 524 Ar₁-4 Ar₂-8 x 525 Ar₁-4 Ar₂-8 x 526 Ar₁-4 Ar₂-8 x 527 Ar₁-4 Ar₂-8 x 528 Ar₁-4 Ar₂-8 x 529 Ar₁-4 Ar₂-8 x 530 Ar₁-4 Ar₂-8 x 531 Ar₁-4 Ar₂-8 x 532 Ar₁-4 Ar₂-8 x 533 Ar₁-4 Ar₂-9 x 534 Ar₁-4 Ar₂-9 x 535 Ar₁-4 Ar₂-9 x 536 Ar₁-4 Ar₂-9 x 537 Ar₁-4 Ar₂-9 x 538 Ar₁-4 Ar₂-9 x 539 Ar₁-4 Ar₂-9 x 540 Ar₁-4 Ar₂-9 x 541 Ar₁-4 Ar₂-9 x 542 Ar₁-4 Ar₂-9 x 543 Ar₁-4 Ar₂-9 x 544 Ar₁-4 Ar₂-9 x 545 Ar₁-4 Ar₂-9 x 546 Ar₁-4 Ar₂- x 547 10 Ar₁-4 Ar₂- x 548 10 Ar₁-4 Ar₂- x 549 10 Ar₁-4 Ar₂- x 550 10 Ar₁-4 Ar₂- x 551 10 Ar₁-4 Ar₂- x 552 10 Ar₁-4 Ar₂- x 553 10 Ar₁-4 Ar₂- x 554 10 Ar₁-4 Ar₂- x 555 10 Ar₁-4 Ar₂- x 556 10 Ar₁-4 Ar₂- x 557 10 Ar₁-4 Ar₂- x 558 10 Ar₁-4 Ar₂- x 559 10 Ar₁-4 Ar₂- x 560 11 Ar₁-4 Ar₂- x 561 11 Ar₁-4 Ar₂- x 562 11 Ar₁-4 Ar₂- x 563 11 Ar₁-4 Ar₂- x 564 11 Ar₁-4 Ar₂- x 565 11 Ar₁-4 Ar₂- x 566 11 Ar₁-4 Ar₂- x 567 11 Ar₁-4 Ar₂- x 568 11 Ar₁-4 Ar₂- x 569 11 Ar₁-4 Ar₂- x 570 11 Ar₁-4 Ar₂- x 571 11 Ar₁-4 Ar₂- x 572 11 Ar₁-4 Ar₂- x 573 12 Ar₁-4 Ar₂- x 574 12 Ar₁-4 Ar₂- x 575 12 Ar₁-4 Ar₂- x 576 12 Ar₁-4 Ar₂- x 577 12 Ar₁-4 Ar₂- x 578 12 Ar₁-4 Ar₂- x 579 12 Ar₁-4 Ar₂- x 580 12 Ar₁-4 Ar₂- x 581 12 Ar₁-4 Ar₂- x 582 12 Ar₁-4 Ar₂- x 583 12 Ar₁-4 Ar₂- x 584 12 Ar₁-4 Ar₂- x 585 12 Ar₁-4 Ar₂- x 586 13 Ar₁-4 Ar₂- x 587 13 Ar₁-4 Ar₂- x 588 13 Ar₁-4 Ar₂- x 589 13 Ar₁-4 Ar₂- x 590 13 Ar₁-4 Ar₂- x 591 13 Ar₁-4 Ar₂- x 592 13 Ar₁-4 Ar₂- x 593 13 Ar₁-4 Ar₂- x 594 13 Ar₁-4 Ar₂- x 595 13 Ar₁-4 Ar₂- x 596 13 Ar₁-4 Ar₂- x 597 13 Ar₁-4 Ar₂- x 598 13 Ar₁-5 Ar₂-5 x 599 Ar₁-5 Ar₂-5 x 600 Ar₁-5 Ar₂-5 x 601 Ar₁-5 Ar₂-5 x 602 Ar₁-5 Ar₂-5 x 603 Ar₁-5 Ar₂-5 x 604 Ar₁-5 Ar₂-5 x 605 Ar₁-5 Ar₂-5 x 606 Ar₁-5 Ar₂-5 x 607 Ar₁-5 Ar₂-5 x 608 Ar₁-5 Ar₂-5 x 609 Ar₁-5 Ar₂-5 x 610 Ar₁-5 Ar₂-5 x 611 Ar₁-5 Ar₂-6 x 612 Ar₁-5 Ar₂-6 x 613 Ar₁-5 Ar₂-6 x 614 Ar₁-5 Ar₂-6 x 615 Ar₁-5 Ar₂-6 x 616 Ar₁-5 Ar₂-6 x 617 Ar₁-5 Ar₂-6 x 618 Ar₁-5 Ar₂-6 x 619 Ar₁-5 Ar₂-6 x 620 Ar₁-5 Ar₂-6 x 621 Ar₁-5 Ar₂-6 x 622 Ar₁-5 Ar₂-6 x 623 Ar₁-5 Ar₂-6 x 624 Ar₁-5 Ar₂-7 x 625 Ar₁-5 Ar₂-7 x 626 Ar₁-5 Ar₂-7 x 627 Ar₁-5 Ar₂-7 x 628 Ar₁-5 Ar₂-7 x 629 Ar₁-5 Ar₂-7 x 630 Ar₁-5 Ar₂-7 x 631 Ar₁-5 Ar₂-7 x 632 Ar₁-5 Ar₂-7 x 633 Ar₁-5 Ar₂-7 x 634 Ar₁-5 Ar₂-7 x 635 Ar₁-5 Ar₂-7 x 636 Ar₁-5 Ar₂-7 x 637 Ar₁-5 Ar₂-8 x 638 Ar₁-5 Ar₂-8 x 639 Ar₁-5 Ar₂-8 x 640 Ar₁-5 Ar₂-8 x 641 Ar₁-5 Ar₂-8 x 642 Ar₁-5 Ar₂-8 x 643 Ar₁-5 Ar₂-8 x 644 Ar₁-5 Ar₂-8 x 645 Ar₁-5 Ar₂-8 x 646 Ar₁-5 Ar₂-8 x 647 Ar₁-5 Ar₂-8 x 648 Ar₁-5 Ar₂-8 x 649 Ar₁-5 Ar₂-8 x 650 Ar₁-5 Ar₂-9 x 651 Ar₁-5 Ar₂-9 x 652 Ar₁-5 Ar₂-9 x 653 Ar₁-5 Ar₂-9 x 654 Ar₁-5 Ar₂-9 x 655 Ar₁-5 Ar₂-9 x 656 Ar₁-5 Ar₂-9 x 657 Ar₁-5 Ar₂-9 x 658 Ar₁-5 Ar₂-9 x 659 Ar₁-5 Ar₂-9 x 660 Ar₁-5 Ar₂-9 x 661 Ar₁-5 Ar₂-9 x 662 Ar₁-5 Ar₂-9 x 663 Ar₁-5 Ar₂- x 664 10 Ar₁-5 Ar₂- x 665 10 Ar₁-5 Ar₂- x 666 10 Ar₁-5 Ar₂- x 667 10 Ar₁-5 Ar₂- x 668 10 Ar₁-5 Ar₂- x 669 10 Ar₁-5 Ar₂- x 670 10 Ar₁-5 Ar₂- x 671 10 Ar₁-5 Ar₂- x 672 10 Ar₁-5 Ar₂- x 673 10 Ar₁-5 Ar₂- x 674 10 Ar₁-5 Ar₂- x 675 10 Ar₁-5 Ar₂- x 676 10 Ar₁-5 Ar₂- x 677 11 Ar₁-5 Ar₂- x 678 11 Ar₁-5 Ar₂- x 679 11 Ar₁-5 Ar₂- x 680 11 Ar₁-5 Ar₂- x 681 11 Ar₁-5 Ar₂- x 682 11 Ar₁-5 Ar₂- x 683 11 Ar₁-5 Ar₂- x 684 11 Ar₁-5 Ar₂- x 685 11 Ar₁-5 Ar₂- x 686 11 Ar₁-5 Ar₂- x 687 11 Ar₁-5 Ar₂- x 688 11 Ar₁-5 Ar₂- x 689 11 Ar₁-5 Ar₂- x 690 12 Ar₁-5 Ar₂- x 691 12 Ar₁-5 Ar₂- x 692 12 Ar₁-5 Ar₂- x 693 12 Ar₁-5 Ar₂- x 694 12 Ar₁-5 Ar₂- x 695 12 Ar₁-5 Ar₂- x 696 12 Ar₁-5 Ar₂- x 697 12 Ar₁-5 Ar₂- x 698 12 Ar₁-5 Ar₂- x 699 12 Ar₁-5 Ar₂- x 700 12 Ar₁-5 Ar₂- x 701 12 Ar₁-5 Ar₂- x 702 12 Ar₁-5 Ar₂- x 703 13 Ar₁-5 Ar₂- x 704 13 Ar₁-5 Ar₂- x 705 13 Ar₁-5 Ar₂- x 706 13 Ar₁-5 Ar₂- x 707 13 Ar₁-5 Ar₂- x 708 13 Ar₁-5 Ar₂- x 709 13 Ar₁-5 Ar₂- x 710 13 Ar₁-5 Ar₂- x 711 13 Ar₁-5 Ar₂- x 712 13 Ar₁-5 Ar₂- x 713 13 Ar₁-5 Ar₂- x 714 13 Ar₁-5 Ar₂- x 715 13 Ar₁-6 Ar₂-6 x 716 Ar₁-6 Ar₂-6 x 717 Ar₁-6 Ar₂-6 x 718 Ar₁-6 Ar₂-6 x 719 Ar₁-6 Ar₂-6 x 720 Ar₁-6 Ar₂-6 x 721 Ar₁-6 Ar₂-6 x 722 Ar₁-6 Ar₂-6 x 723 Ar₁-6 Ar₂-6 x 724 Ar₁-6 Ar₂-6 x 725 Ar₁-6 Ar₂-6 x 726 Ar₁-6 Ar₂-6 x 727 Ar₁-6 Ar₂-6 x 728 Ar₁-6 Ar₂-7 x 729 Ar₁-6 Ar₂-7 x 730 Ar₁-6 Ar₂-7 x 731 Ar₁-6 Ar₂-7 x 732 Ar₁-6 Ar₂-7 x 733 Ar₁-6 Ar₂-7 x 734 Ar₁-6 Ar₂-7 x 735 Ar₁-6 Ar₂-7 x 736 Ar₁-6 Ar₂-7 x 737 Ar₁-6 Ar₂-7 x 738 Ar₁-6 Ar₂-7 x 739 Ar₁-6 Ar₂-7 x 740 Ar₁-6 Ar₂-7 x 741 Ar₁-6 Ar₂-8 x 742 Ar₁-6 Ar₂-8 x 743 Ar₁-6 Ar₂-8 x 744 Ar₁-6 Ar₂-8 x 745 Ar₁-6 Ar₂-8 x 746 Ar₁-6 Ar₂-8 x 747 Ar₁-6 Ar₂-8 x 748 Ar₁-6 Ar₂-8 x 749 Ar₁-6 Ar₂-8 x 750 Ar₁-6 Ar₂-8 x 751 Ar₁-6 Ar₂-8 x 752 Ar₁-6 Ar₂-8 x 753 Ar₁-6 Ar₂-8 x 754 Ar₁-6 Ar₂-9 x 755 Ar₁-6 Ar₂-9 x 756 Ar₁-6 Ar₂-9 x 757 Ar₁-6 Ar₂-9 x 758 Ar₁-6 Ar₂-9 x 759 Ar₁-6 Ar₂-9 x 760 Ar₁-6 Ar₂-9 x 761 Ar₁-6 Ar₂-9 x 762 Ar₁-6 Ar₂-9 x 763 Ar₁-6 Ar₂-9 x 764 Ar₁-6 Ar₂-9 x 765 Ar₁-6 Ar₂-9 x 766 Ar₁-6 Ar₂-9 x 767 Ar₁-6 Ar₂- x 768 10 Ar₁-6 Ar₂- x 769 10 Ar₁-6 Ar₂- x 770 10 Ar₁-6 Ar₂- x 771 10 Ar₁-6 Ar₂- x 772 10 Ar₁-6 Ar₂- x 773 10 Ar₁-6 Ar₂- x 774 10 Ar₁-6 Ar₂- x 775 10 Ar₁-6 Ar₂- x 776 10 Ar₁-6 Ar₂- x 777 10 Ar₁-6 Ar₂- x 778 10 Ar₁-6 Ar₂- x 779 10 Ar₁-6 Ar₂- x 780 10 Ar₁-6 Ar₂- x 781 11 Ar₁-6 Ar₂- x 782 11 Ar₁-6 Ar₂- x 783 11 Ar₁-6 Ar₂- x 784 11 Ar₁-6 Ar₂- x 785 11 Ar₁-6 Ar₂- x 786 11 Ar₁-6 Ar₂- x 787 11 Ar₁-6 Ar₂- x 788 11 Ar₁-6 Ar₂- x 789 11 Ar₁-6 Ar₂- x 790 11 Ar₁-6 Ar₂- x 791 11 Ar₁-6 Ar₂- x 792 11 Ar₁-6 Ar₂- x 793 11 Ar₁-6 Ar₂- x 794 12 Ar₁-6 Ar₂- x 795 12 Ar₁-6 Ar₂- x 796 12 Ar₁-6 Ar₂- x 797 12 Ar₁-6 Ar₂- x 798 12 Ar₁-6 Ar₂- x 799 12 Ar₁-6 Ar₂- x 800 12 Ar₁-6 Ar₂- x 801 12 Ar₁-6 Ar₂- x 802 12 Ar₁-6 Ar₂- x 803 12 Ar₁-6 Ar₂- x 804 12 Ar₁-6 Ar₂- x 805 12 Ar₁-6 Ar₂- x 806 12 Ar₁-6 Ar₂- x 807 13 Ar₁-6 Ar₂- x 808 13 Ar₁-6 Ar₂- x 809 13 Ar₁-6 Ar₂- x 810 13 Ar₁-6 Ar₂- x 811 13 Ar₁-6 Ar₂- x 812 13 Ar₁-6 Ar₂- x 813 13 Ar₁-6 Ar₂- x 814 13 Ar₁-6 Ar₂- x 815 13 Ar₁-6 Ar₂- x 816 13 Ar₁-6 Ar₂- x 817 13 Ar₁-6 Ar₂- x 818 13 Ar₁-6 Ar₂- x 819 13 Ar₁-7 Ar₂-7 x 820 Ar₁-7 Ar₂-7 x 821 Ar₁-7 Ar₂-7 x 822 Ar₁-7 Ar₂-7 x 823 Ar₁-7 Ar₂-7 x 824 Ar₁-7 Ar₂-7 x 825 Ar₁-7 Ar₂-7 x 826 Ar₁-7 Ar₂-7 x 827 Ar₁-7 Ar₂-7 x 828 Ar₁-7 Ar₂-7 x 829 Ar₁-7 Ar₂-7 x 830 Ar₁-7 Ar₂-7 x 831 Ar₁-7 Ar₂-7 x 832 Ar₁-7 Ar₂-8 x 833 Ar₁-7 Ar₂-8 x 834 Ar₁-7 Ar₂-8 x 835 Ar₁-7 Ar₂-8 x 836 Ar₁-7 Ar₂-8 x 837 Ar₁-7 Ar₂-8 x 838 Ar₁-7 Ar₂-8 x 839 Ar₁-7 Ar₂-8 x 840 Ar₁-7 Ar₂-8 x 841 Ar₁-7 Ar₂-8 x 842 Ar₁-7 Ar₂-8 x 843 Ar₁-7 Ar₂-8 x 844 Ar₁-7 Ar₂-8 x 845 Ar₁-7 Ar₂-9 x 846 Ar₁-7 Ar₂-9 x 847 Ar₁-7 Ar₂-9 x 848 Ar₁-7 Ar₂-9 x 849 Ar₁-7 Ar₂-9 x 850 Ar₁-7 Ar₂-9 x 851 Ar₁-7 Ar₂-9 x 852 Ar₁-7 Ar₂-9 x 853 Ar₁-7 Ar₂-9 x 854 Ar₁-7 Ar₂-9 x 855 Ar₁-7 Ar₂-9 x 856 Ar₁-7 Ar₂-9 x 857 Ar₁-7 Ar₂-9 x 858 Ar₁-7 Ar₂- x 859 10 Ar₁-7 Ar₂- x 860 10 Ar₁-7 Ar₂- x 861 10 Ar₁-7 Ar₂- x 862 10 Ar₁-7 Ar₂- x 863 10 Ar₁-7 Ar₂- x 864 10 Ar₁-7 Ar₂- x 865 10 Ar₁-7 Ar₂- x 866 10 Ar₁-7 Ar₂- x 867 10 Ar₁-7 Ar₂- x 868 10 Ar₁-7 Ar₂- x 869 10 Ar₁-7 Ar₂- x 870 10 Ar₁-7 Ar₂- x 871 10 Ar₁-7 Ar₂- x 872 11 Ar₁-7 Ar₂- x 873 11 Ar₁-7 Ar₂- x 874 11 Ar₁-7 Ar₂- x 875 11 Ar₁-7 Ar₂- x 876 11 Ar₁-7 Ar₂- x 877 11 Ar₁-7 Ar₂- x 878 11 Ar₁-7 Ar₂- x 879 11 Ar₁-7 Ar₂- x 880 11 Ar₁-7 Ar₂- x 881 11 Ar₁-7 Ar₂- x 882 11 Ar₁-7 Ar₂- x 883 11 Ar₁-7 Ar₂- x 884 11 Ar₁-7 Ar₂- x 885 12 Ar₁-7 Ar₂- x 886 12 Ar₁-7 Ar₂- x 887 12 Ar₁-7 Ar₂- x 888 12 Ar₁-7 Ar₂- x 889 12 Ar₁-7 Ar₂- x 890 12 Ar₁-7 Ar₂- x 891 12 Ar₁-7 Ar₂- x 892 12 Ar₁-7 Ar₂- x 893 12 Ar₁-7 Ar₂- x 894 12 Ar₁-7 Ar₂- x 895 12 Ar₁-7 Ar₂- x 896 12 Ar₁-7 Ar₂- x 897 12 Ar₁-7 Ar₂- x 898 13 Ar₁-7 Ar₂- x 899 13 Ar₁-7 Ar₂- x 900 13 Ar₁-7 Ar₂- x 901 13 Ar₁-7 Ar₂- x 902 13 Ar₁-7 Ar₂- x 903 13 Ar₁-7 Ar₂- x 904 13 Ar₁-7 Ar₂- x 905 13 Ar₁-7 Ar₂- x 906 13 Ar₁-7 Ar₂- x 907 13 Ar₁-7 Ar₂- x 908 13 Ar₁-7 Ar₂- x 909 13 Ar₁-7 Ar₂- x 910 13 Ar₁-8 Ar₂-8 x 911 Ar₁-8 Ar₂-8 x 912 Ar₁-8 Ar₂-8 x 913 Ar₁-8 Ar₂-8 x 914 Ar₁-8 Ar₂-8 x 915 Ar₁-8 Ar₂-8 x 916 Ar₁-8 Ar₂-8 x 917 Ar₁-8 Ar₂-8 x 918 Ar₁-8 Ar₂-8 x 919 Ar₁-8 Ar₂-8 x 920 Ar₁-8 Ar₂-8 x 921 Ar₁-8 Ar₂-8 x 922 Ar₁-8 Ar₂-8 x 923 Ar₁-8 Ar₂-9 x 924 Ar₁-8 Ar₂-9 x 925 Ar₁-8 Ar₂-9 x 926 Ar₁-8 Ar₂-9 x 927 Ar₁-8 Ar₂-9 x 928 Ar₁-8 Ar₂-9 x 929 Ar₁-8 Ar₂-9 x 930 Ar₁-8 Ar₂-9 x 931 Ar₁-8 Ar₂-9 x 932 Ar₁-8 Ar₂-9 x 933 Ar₁-8 Ar₂-9 x 934 Ar₁-8 Ar₂-9 x 935 Ar₁-8 Ar₂-9 x 936 Ar₁-8 Ar₂- x 937 10 Ar₁-8 Ar₂- x 938 10 Ar₁-8 Ar₂- x 939 10 Ar₁-8 Ar₂- x 940 10 Ar₁-8 Ar₂- x 941 10 Ar₁-8 Ar₂- x 942 10 Ar₁-8 Ar₂- x 943 10 Ar₁-8 Ar₂- x 944 10 Ar₁-8 Ar₂- x 945 10 Ar₁-8 Ar₂- x 946 10 Ar₁-8 Ar₂- x 947 10 Ar₁-8 Ar₂- x 948 10 Ar₁-8 Ar₂- x 949 10 Ar₁-8 Ar₂- x 950 11 Ar₁-8 Ar₂- x 951 11 Ar₁-8 Ar₂- x 952 11 Ar₁-8 Ar₂- x 953 11 Ar₁-8 Ar₂- x 954 11 Ar₁-8 Ar₂- x 955 11 Ar₁-8 Ar₂- x 956 11 Ar₁-8 Ar₂- x 957 11 Ar₁-8 Ar₂- x 958 11 Ar₁-8 Ar₂- x 959 11 Ar₁-8 Ar₂- x 960 11 Ar₁-8 Ar₂- x 961 11 Ar₁-8 Ar₂- x 962 11 Ar₁-8 Ar₂- x 963 12 Ar₁-8 Ar₂- x 964 12 Ar₁-8 Ar₂- x 965 12 Ar₁-8 Ar₂- x 966 12 Ar₁-8 Ar₂- x 967 12 Ar₁-8 Ar₂- x 968 12 Ar₁-8 Ar₂- x 969 12 Ar₁-8 Ar₂- x 970 12 Ar₁-8 Ar₂- x 971 12 Ar₁-8 Ar₂- x 972 12 Ar₁-8 Ar₂- x 973 12 Ar₁-8 Ar₂- x 974 12 Ar₁-8 Ar₂- x 975 12 Ar₁-8 Ar₂- x 976 13 Ar₁-8 Ar₂- x 977 13 Ar₁-8 Ar₂- x 978 13 Ar₁-8 Ar₂- x 979 13 Ar₁-8 Ar₂- x 980 13 Ar₁-8 Ar₂- x 981 13 Ar₁-8 Ar₂- x 982 13 Ar₁-8 Ar₂- x 983 13 Ar₁-8 Ar₂- x 984 13 Ar₁-8 Ar₂- x 985 13 Ar₁-8 Ar₂- x 986 13 Ar₁-8 Ar₂- x 987 13 Ar₁-8 Ar₂- x 988 13 Ar₁9 Ar₂-9 x 989 Ar₁9 Ar₂-9 x 990 Ar₁9 Ar₂-9 x 991 Ar₁9 Ar₂-9 x 992 Ar₁9 Ar₂-9 x 993 Ar₁9 Ar₂-9 x 994 Ar₁9 Ar₂-9 x 995 Ar₁9 Ar₂-9 x 996 Ar₁9 Ar₂-9 x 997 Ar₁9 Ar₂-9 x 998 Ar₁9 Ar₂-9 x 999 Ar₁9 Ar₂-9 x 1000 Ar₁9 Ar₂-9 x 1001 Ar₁9 Ar₂- x 1002 10 Ar₁9 Ar₂- x 1003 10 Ar₁9 Ar₂- x 1004 10 Ar₁9 Ar₂- x 1005 10 Ar₁9 Ar₂- x 1006 10 Ar₁9 Ar₂- x 1007 10 Ar₁9 Ar₂- x 1008 10 Ar₁9 Ar₂- x 1009 10 Ar₁9 Ar₂- x 1010 10 Ar₁9 Ar₂- x 1011 10 Ar₁9 Ar₂- x 1012 10 Ar₁9 Ar₂- x 1013 10 Ar₁9 Ar₂- x 1014 10 Ar₁9 Ar₂- x 1015 11 Ar₁9 Ar₂- x 1016 11 Ar₁9 Ar₂- x 1017 11 Ar₁9 Ar₂- x 1018 11 Ar₁9 Ar₂- x 1019 11 Ar₁9 Ar₂- x 1020 11 Ar₁9 Ar₂- x 1021 11 Ar₁9 Ar₂- x 1022 11 Ar₁9 Ar₂- x 1023 11 Ar₁9 Ar₂- x 1024 11 Ar₁9 Ar₂- x 1025 11 Ar₁9 Ar₂- x 1026 11 Ar₁9 Ar₂- x 1027 11 Ar₁9 Ar₂- x 1028 12 Ar₁9 Ar₂- x 1029 12 Ar₁9 Ar₂- x 1030 12 Ar₁9 Ar₂- x 1031 12 Ar₁9 Ar₂- x 1032 12 Ar₁9 Ar₂- x 1033 12 Ar₁9 Ar₂- x 1034 12 Ar₁9 Ar₂- x 1035 12 Ar₁9 Ar₂- x 1036 12 Ar₁9 Ar₂- x 1037 12 Ar₁9 Ar₂- x 1038 12 Ar₁9 Ar₂- x 1039 12 Ar₁9 Ar₂- x 1040 12 Ar₁9 Ar₂- x 1041 13 Ar₁9 Ar₂- x 1042 13 Ar₁9 Ar₂- x 1043 13 Ar₁9 Ar₂- x 1044 13 Ar₁9 Ar₂- x 1045 13 Ar₁9 Ar₂- x 1046 13 Ar₁9 Ar₂- x 1047 13 Ar₁9 Ar₂- x 1048 13 Ar₁9 Ar₂- x 1049 13 Ar₁9 Ar₂- x 1050 13 Ar₁9 Ar₂- x 1051 13 Ar₁9 Ar₂- x 1052 13 Ar₁9 Ar₂- x 1053 13 Ar₁10 Ar₂- x 1054 10 Ar₁10 Ar₂- x 1055 10 Ar₁10 Ar₂- x 1056 10 Ar₁10 Ar₂- x 1057 10 Ar₁10 Ar₂- x 1058 10 Ar₁10 Ar₂- x 1059 10 Ar₁10 Ar₂- x 1060 10 Ar₁10 Ar₂- x 1061 10 Ar₁10 Ar₂- x 1062 10 Ar₁10 Ar₂- x 1063 10 Ar₁10 Ar₂- x 1064 10 Ar₁10 Ar₂- x 1065 10 Ar₁10 Ar₂- x 1066 10 Ar₁10 Ar₂- x 1067 11 Ar₁10 Ar₂- x 1068 11 Ar₁10 Ar₂- x 1069 11 Ar₁10 Ar₂- x 1070 11 Ar₁10 Ar₂- x 1071 11 Ar₁10 Ar₂- x 1072 11 Ar₁10 Ar₂- x 1073 11 Ar₁10 Ar₂- x 1074 11 Ar₁10 Ar₂- x 1075 11 Ar₁10 Ar₂- x 1076 11 Ar₁10 Ar₂- x 1077 11 Ar₁10 Ar₂- x 1078 11 Ar₁10 Ar₂- x 1079 11 Ar₁10 Ar₂- x 1080 12 Ar₁10 Ar₂- x 1081 12 Ar₁10 Ar₂- x 1082 12 Ar₁10 Ar₂- x 1083 12 Ar₁10 Ar₂- x 1084 12 Ar₁10 Ar₂- x 1085 12 Ar₁10 Ar₂- x 1086 12 Ar₁10 Ar₂- x 1087 12 Ar₁10 Ar₂- x 1088 12 Ar₁10 Ar₂- x 1089 12 Ar₁10 Ar₂- x 1090 12 Ar₁10 Ar₂- x 1091 12 Ar₁10 Ar₂- x 1092 12 Ar₁10 Ar₂- x 1093 13 Ar₁10 Ar₂- x 1094 13 Ar₁10 Ar₂- x 1095 13 Ar₁10 Ar₂- x 1096 13 Ar₁10 Ar₂- x 1097 13 Ar₁10 Ar₂- x 1098 13 Ar₁10 Ar₂- x 1099 13 Ar₁10 Ar₂- x 1100 13 Ar₁10 Ar₂- x 1101 13 Ar₁10 Ar₂- x 1102 13 Ar₁10 Ar₂- x 1103 13 Ar₁10 Ar₂- x 1104 13 Ar₁10 Ar₂- x 1105 13 Ar₁11 Ar₂- x 1106 11 Ar₁11 Ar₂- x 1107 11 Ar₁11 Ar₂- x 1108 11 Ar₁11 Ar₂- x 1109 11 Ar₁11 Ar₂- x 1110 11 Ar₁11 Ar₂- x 1111 11 Ar₁11 Ar₂- x 1112 11 Ar₁11 Ar₂- x 1113 11 Ar₁11 Ar₂- x 1114 11 Ar₁11 Ar₂- x 1115 11 Ar₁11 Ar₂- x 1116 11 Ar₁11 Ar₂- x 1117 11 Ar₁11 Ar₂- x 1118 11 Ar₁11 Ar₂- x 1119 12 Ar₁11 Ar₂- x 1120 12 Ar₁11 Ar₂- x 1121 12 Ar₁11 Ar₂- x 1122 12 Ar₁11 Ar₂- x 1123 12 Ar₁11 Ar₂- x 1124 12 Ar₁11 Ar₂- x 1125 12 Ar₁11 Ar₂- x 1126 12 Ar₁11 Ar₂- x 1127 12 Ar₁11 Ar₂- x 1128 12 Ar₁11 Ar₂- x 1129 12 Ar₁11 Ar₂- x 1130 12 Ar₁11 Ar₂- x 1131 12 Ar₁11 Ar₂- x 1132 13 Ar₁11 Ar₂- x 1133 13 Ar₁11 Ar₂- x 1134 13 Ar₁11 Ar₂- x 1135 13 Ar₁11 Ar₂- x 1136 13 Ar₁11 Ar₂- x 1137 13 Ar₁11 Ar₂- x 1138 13 Ar₁11 Ar₂- x 1139 13 Ar₁11 Ar₂- x 1140 13 Ar₁11 Ar₂- x 1141 13 Ar₁11 Ar₂- x 1142 13 Ar₁11 Ar₂- x 1143 13 Ar₁11 Ar₂- x 1144 13 Ar₁12 Ar₂- x 1145 12 Ar₁12 Ar₂- x 1146 12 Ar₁12 Ar₂- x 1147 12 Ar₁12 Ar₂- x 1148 12 Ar₁12 Ar₂- x 1149 12 Ar₁12 Ar₂- x 1150 12 Ar₁12 Ar₂- x 1151 12 Ar₁12 Ar₂- x 1152 12 Ar₁12 Ar₂- x 1153 12 Ar₁12 Ar₂- x 1154 12 Ar₁12 Ar₂- x 1155 12 Ar₁12 Ar₂- x 1156 12 Ar₁12 Ar₂- x 1157 12 Ar₁12 Ar₂- x 1158 13 Ar₁12 Ar₂- x 1159 13 Ar₁12 Ar₂- x 1160 13 Ar₁12 Ar₂- x 1161 13 Ar₁12 Ar₂- x 1162 13 Ar₁12 Ar₂- x 1163 13 Ar₁12 Ar₂- x 1164 13 Ar₁12 Ar₂- x 1165 13 Ar₁12 Ar₂- x 1166 13 Ar₁12 Ar₂- x 1167 13 Ar₁12 Ar₂- x 1168 13 Ar₁12 Ar₂- x 1169 13 Ar₁12 Ar₂- x 1170 13 Ar₁13 Ar₂- x 1171 13 Ar₁13 Ar₂- x 1172 13 Ar₁13 Ar₂- x 1173 13 Ar₁13 Ar₂- x 1174 13 Ar₁13 Ar₂- x 1175 13 Ar₁13 Ar₂- x 1176 13 Ar₁13 Ar₂- x 1177 13 Ar₁13 Ar₂- x 1178 13 Ar₁13 Ar₂- x 1179 13 Ar₁13 Ar₂- x 1180 13 Ar₁13 Ar₂- x 1181 13 Ar₁13 Ar₂- x 1182 13 Ar₁13 Ar₂- x 1183 13

In one embodiment, a first device is provided. The first device comprises an organic light emitting device, further comprising: an anode, a cathode, a hole injection layer disposed between the anode and the emissive layer, a first hole transport layer disposed between the hole injection layer and the emissive layer, and a second hole transport layer disposed between the first hole transport layer and the emissive layer, and wherein the second hole transport layer comprises a compound of formula:

In the compound of Formula II, Ar₁, Ar₂, and Ar₅ are independently selected from the group consisting of aryl and heteroaryl and R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

As used herein, a hole transporting layer (HTL) in an OLED can be disposed between the and anode and the emissive layer. It is preferred that the HTL is relatively hole conductive, which helps avoid high operating voltage. In order to achieve high hole conductivity, high hole mobility materials are used. These materials are usually triarylamine compounds. These compounds may have HOMO/LUMO levels and/or triplet energy which are not compatible with the emissive layer for optimum device performance and lifetime. On the other hand, in order to have an HTL with more compatible HOMO/LUMO levels and/or triplet energy, hole mobility may be compromised.

In order to achieve a low voltage, higher device performance and lifetime device, the introduction of a secondary hole transporting layer, in addition to the primary hole transporting layer has been demonstrated and shown to be effective. The primary hole transporting layer is largely responsible for hole transport. The secondary hole transporting layer, sandwiched between the primary hole transporting layer and the emissive layer, functions as a bridging layer. The thickness of the secondary hole transport layer is preferably low in order to not significantly increase the operating voltage. However, the hole injection from the secondary hole transporting layer to the emissive layer, charge confinement and exciton confinement between the secondary hole transporting layer and the emissive layer are controlled by the energy levels and single/triplet energy of the secondary hole transporting layer. Since the secondary hole transporting layer thickness is low, there is relatively little concern about the hole mobility. This allows for a higher flexibility in the design of materials with appropriate energy levels and single/triplet energy to function well with the emissive layer.

It has surprisingly been discovered that compounds of Formula I and Formula II are useful materials in the secondary hole transporting layer. In the compounds of Formula I, the most electron rich portion of the molecule is the N(Ar₁)(Ar₂) group. Without being bound by theory, this part is believed to be mostly responsible for the hole transport.

The carbazole-N—Ar₅ moiety may be less electron rich and may provide a relatively accessible LUMO level and π-conjugation to stabilize radical anions if the material is reduced. In particular, Ar₅ is preferably a high triplet fused-ring aromatic as disclosed herein. In some embodiments, Ar₅ can be triphenylene or heteroaromatic group such as dibenzofuran, dibenzothiophene and dibenzoselenophene. It has been discovered that the aforementioned substitution pattern for Ar₁, Ar₂, and Ar₅ can render compounds with high triplet energy and significant charge stabilization.

In one embodiment, the compound has the formula:

wherein X is selected from the group consisting of O, S, and Se, wherein R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, the second hole transport layer is disposed adjacent to the first hole transport layer. By “adjacent” it is meant that the second hole transport layer is physically in contact with the first hole transport layer. In one embodiment, the first hole transport layer is thicker than the second hole transport layer. In one embodiment, the first hole transport layer comprises a compound with the formula:

wherein Ar_(a), Ar_(b), Ar_(c) and Ar_(d) are independently selected from the group consisting of aryl and heteroaryl.

In one embodiment, the triplet energy of the compound of Formula II is higher than the emission energy of the emissive layer.

In one embodiment, Ar₁, Ar₂ and Ar₅ are independently selected from the group consisting of:

In one embodiment, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one embodiment, Ar₁ and Ar₂ are independently selected from the group consisting of:

In one embodiment, the first device further comprises a first dopant material that is an emissive dopant comprising a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein R_(a), R_(b), R_(c), and R_(d) may represent mono, di, tri, or tetra substitution, or no substitution and wherein R_(a), R_(b), R_(c), and R_(d) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and wherein two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) are optionally joined to form a fused ring or form a multidentate ligand.

In one embodiment, the first device is a consumer product. In one embodiment, the first device is an organic light-emitting device. In one embodiment, the first device comprises a lighting panel. In one embodiment, a first device comprising an organic light emitting device, further comprising an anode, a cathode, a first organic layer disposed between the anode and the cathode, and wherein the first organic layer comprises a compound of formula:

In the compound of Formula I, Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl, X is selected from the group consisting of O, S, and Se, R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution, and R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one embodiment, the first organic layer is an emissive layer. In one embodiment, the emissive layer is a phosphorescent emissive layer.

Device Examples

All OLED device examples were fabricated by high vacuum (<10⁻⁷ Torr) thermal evaporation (VTE). The anode electrode is ˜800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) and a moisture getter was incorporated inside the package.

The organic stack of the Device Examples in Table 2 consists of sequentially, from the ITO surface, 100 Å of LG101 (purchased from LG Chem) as the hole injection layer (HIL), 500 Å of NPD as the primary hole transporting layer (HTL), 50 Å of the secondary hole transporting layer, 300 Å of Compound A doped with 10% or 12% of phosphorescent dopant Compound B as the emissive layer (EML), 50 Å of Compound A as the ETL2 and 450 Å of Alq₃ as the ETL1.

Comparative Example 1 was fabricated in the same way except that there was no secondary hole transporting layer, and the thickness of the primary hole transporting layer was increased to 550 Å to match the combined thickness of the primary and secondary hole transporting layers in the Device Examples.

The structures of the aforementioned device components are as follows:

TABLE 2 Device performance summary. At L = 1000 cd/m² At J = 40 mA/cm² Secondary 1931 CIE Voltage LE EQE PE L₀ LT₈₀ Example HTL [50 Å] EML [300 Å] x y [V] [cd/A] [%] [lm/W] [cd/m²] [h] Device Compound Compound A: 0.330 0.624 4.9 76.5 20.9 49.0 25338 200 Example 1 113 Compound B 12% Device Compound Compound A: 0.322 0.629 4.8 76.3 20.9 50.3 25112 422 Example 2 178 Compound B 10% Device Compound Compound A: 0.322 0.629 4.7 75.5 20.7 50.3 24932 420 Example 3 182 Compound B 10% Comparative none Compound A: 0.327 0.626 4.9 68.1 18.6 43.8 19596 290 Device Compound B Example 1 12%

Device Examples 1-3 are the same as Comparative Device Example 1 except for the presence of the secondary HTL in former and the absence of the secondary HTL in latter. Device Examples 1-3 have Compounds 113, 178 and 182 respectively as the secondary HTL. The efficiencies of Device Examples 1-3 are higher (EQE=20.7-20.9%) than the efficiency of Comparative Device Example 1 (EQE=18.6%). The operation lifetimes of Device Examples 2 and 3 are remarkably high. The LT₈₀, the time required for the initial luminance (L₀) to drop to 80% of its initial value, at a constant current density of 40 mA/cm², is ˜420 h, compared to 290 h of Comparative Device Example 1. Without being bound by theory, the improved efficiency and lifetime when Compounds 178 and 182 are used as the secondary HTL may be due to the high triplet energy, providing improved exciton confinement; the presence of a dibenzothiophene or triphenylene group, providing a high triplet, charge stabilization moiety; and a sufficiently shallow HOMO level (Compound 178 HOMO=−5.23 eV, Compound 182 HOMO=−5.21 eV, NPD HOMO=−5.17 eV) for hole transport.

Although hole conductivity may be reduced in compounds of Formula I or Formula II with respect to traditionally used triarylamine compounds such as NPD, compounds of Formula I and Formula II that bear substituents such as

(Group 1) at the Ar₁ and Ar₂ positions have better hole mobility that compounds bearing substituents such as

(Group 2) at these same positions because the latter group of substituents, deepens the HOMO levels, which causes a larger increase in hole conductivity. Additionally, although device lifetimes for a given thickness of the secondary HTL are sometimes reduced for compounds bearing Group 2 substituents compared with Group 1 substituents, this difference can be mitigated by decreasing the thickness of the secondary HTL.

The HOMO and LUMO levels and triplet energy are summarized in Table 3. The LT₈₀ of Device Example 1 with Compound 113 as the secondary HTL is 200 h, less stable than Device Example 1 (422 h) with Compound 178 as the secondary HTL. The difference between Compound 113 and Compound 178 is the N(Ar₁)(Ar₂) group. In general, if the N is connected to a dibenzofuran or dibenzothiphene group, the HOMO gets deeper (Compound 1 HOMO=−5.31 eV, NPD HOMO=−5.17 eV) and hole conductivity may be reduced. This may lead to shorter device operation lifetime if the hole conductivity of the secondary HTL is not high enough, even though its thickness is kept low.

TABLE 3 HOMO, LUMO levels and triplet energy Compound HOMO (eV) * LUMO (eV) * Triplet energy (nm)^(#) NPD −5.17 −1.98 500 Compound 113 −5.31 −1.98 436 Compound 178 −5.23 −1.99 450 Compound 182 −5.21 −2.04 450 ^(*) By solution electrochemistry using ferrocene as the standard ^(#)By DTF/B3LYP/6-31g(d) optimized geometry

COMBINATION WITH OTHER MATERIALS

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but not limit to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each Ar is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

k is an integer from 1 to 20; X¹ to X⁸ is C (including CH) or N; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but not limit to the following general formula:

M is a metal, having an atomic weight greater than 40; (Y¹-Y²) is a bidentate ligand, Y¹ and Y² are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹-Y²) is a 2-phenylpyridine derivative.

In another aspect, (Y¹-Y²) is a carbene ligand.

In another aspect, M is selected from Ir, Pt, Os, and Zn.

In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Host:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly energy of the host is larger than that of the dopant. While the Table below categorizes host materials as preferred for devices that emit various colors, any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

M is a metal; (Y³-Y⁴) is a bidentate ligand, Y³ and Y⁴ are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and m+n is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

(O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, M is selected from Ir and Pt.

In a further aspect, (Y³-Y⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the group consisting aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

R¹ to R⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

Z¹ and Z² is selected from NR¹, O, or S.

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

k is an integer from 0 to 20; L is an ancillary ligand, m is an integer from 1 to 3.

ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

R¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above.

Ar¹ to Ar³ has the similar definition as Ar's mentioned above.

k is an integer from 0 to 20.

X¹ to X⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:

(O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L is an ancillary ligand; m is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated.

In addition to and/or in combination with the materials disclosed herein, many hole injection materials, hole transporting materials, host materials, dopant materials, exiton/hole blocking layer materials, electron transporting and electron injecting materials may be used in an OLED. Non-limiting examples of the materials that may be used in an OLED in combination with materials disclosed herein are listed in Table 4 below. Table 4 lists non-limiting classes of materials, non-limiting examples of compounds for each class, and references that disclose the materials.

TABLE 4 MATERIAL EXAMPLES OF MATERIAL PUBLICATIONS Hole injection materials Phthalocyanine and porphyrin compounds

Appl. Phys. Lett. 69, 2160 (1996) Starburst triarylamines

J. Lumin. 72-74, 985 (1997) CF_(x) Fluorohydrocarbon polymer

Appl. Phys. Lett. 78, 673 (2001) Conducting polymers (e.g., PEDOT:PSS, polyaniline, polythiophene)

Synth. Met. 87, 171 (1997) WO2007002683 Phosphonic acid and silane SAMs

US20030162053 Triarylamine or polythiophene polymers with conductivity dopants

  and  

 

EP1725079A1 Organic compounds with conductive inorganic compounds, such as molybdenum and tungsten oxides

US20050123751 SID Symposium Digest, 37, 923 (2006) WO2009018009 n-type semiconducting organic complexes

US20020158242 Metal organometallic complexes

US20060240279 Cross-linkable compounds

US20080220265 Polythiophene based polymers and copolymers

WO 2011075644 EP2350216 Hole transporting materials Triarylamines (e.g., TPD, α-NPD)

Appl. Phys. Lett. 51, 913 (1987)

U.S. Pat. No. 5,061,569

EP650955

J. Mater. Chem. 3, 319 (1993)

Appl. Phys. Lett. 90, 183503 (2007)

Appl. Phys. Lett. 90, 183503 (2007) Triarylamine on spirofluorene core

Synth. Met. 91, 209 (1997) Arylamine carbazole compounds

Adv. Mater. 6, 677 (1994), US20080124572 Triarylamine with (di)benzothiophene/ (di)benzofuran

US20070278938, US20080106190, US20110163302 Indolocarbazoles

Synth. Met. 111, 421 (2000) Isoindole compounds

Chem. Mater. 15, 3148 (2003) Metal carbene complexes

US20080018221 Phosphorescent OLED host materials Red hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001) Metal 8-hydroxyquinolates (e.g., Alq₃, BAlq)

Nature 395, 151 (1998)

US20060202194

WO2005014551

WO2006072002 Metal phenoxybenzothiazole compounds

Appl. Phys. Lett. 90, 123509 (2007) Conjugated oligomers and polymers (e.g., polyfluorene)

Org. Electron. 1, 15 (2000) Aromatic fused rings

WO2009066779, WO2009066778, WO2009063833, US20090045731, US20090045730, WO2009008311, US20090008605, US20090009065 Zinc complexes

WO2010056066 Chrysene based compounds

WO2011086863 Green hosts Arylcarbazoles

Appl. Phys. Lett. 78, 1622 (2001)

US20030175553

WO2001039234 Aryltriphenylene compounds

US20060280965

US20060280965

WO2009021126 Poly-fused heteroaryl compounds

US20090309488 US20090302743 US20100012931 Donor acceptor type molecules

WO2008056746

WO2010107244 Aza-carbazole/DBT/DBF

JP2008074939

US20100187984 Polymers (e.g., PVK)

Appl. Phys. Lett. 77, 2280 (2000) Spirofluorene compounds

WO2004093207 Metal phenoxybenzooxazole compounds

WO2005089025

WO2006132173

JP200511610 Spirofluorene-carbazole compounds

JP2007254297

JP2007254297 Indolocarbazoles

WO2007063796

WO2007063754 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole)

J. Appl. Phys. 90, 5048 (2001)

WO2004107822 Tetraphenylene complexes

US20050112407 Metal phenoxypyridine compounds

WO2005030900 Metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands)

US20040137268, US20040137267 Blue hosts Arylcarbazoles

Appl. Phys. Lett, 82, 2422 (2003)

US20070190359 Dibenzothiophene/ Dibenzofuran-carbazole compounds

WO2006114966, US20090167162

US20090167162

WO2009086028

US20090030202, US20090017330

US20100084966 Silicon aryl compounds

US20050238919

WO2009003898 Silicon/Germanium aryl compounds

EP2034538A Aryl benzoyl ester

WO2006100298 Carbazole linked by non- conjugated groups

US20040115476 Aza-carbazoles

US20060121308 High triplet metal organometallic complex

U.S. Pat. No. 7,154,114 Phosphorescent dopants Red dopants Heavy metal porphyrins (e.g., PtOEP)

Nature 395, 151 (1998) Iridium(III) organometallic complexes

Appl. Phys. Lett. 78, 1622 (2001)

US2006835469

US2006835469

US20060202194

US20060202194

US20070087321

US20080261076 US20100090591

US20070087321

Adv. Mater. 19, 739 (2007)

WO2009100991

WO2008101842

U.S. Pat. No. 7,232,618 Platinum(II) organometallic complexes

WO2003040257

US20070103060 Osmium(III) complexes

Chem. Mater. 17, 3532 (2005) Ruthenium(II) complexes

Adv. Mater. 17, 1059 (2005) Rhenium (I), (II), and (III) complexes

US20050244673 Green dopants Iridium(III) organometallic complexes

  and its derivatives Inorg. Chem. 40, 1704 (2001)

US20020034656

U.S. Pat. No. 7,332,232

US20090108737

WO2010028151

EP1841834B

US20060127696

US20090039776

U.S. Pat. No. 6,921,915

US20100244004

U.S. Pat. No. 6,687,266

Chem. Mater. 16, 2480 (2004)

US20070190359

US 20060008670 JP2007123392

WO2010086089, WO2011044988

Adv. Mater. 16, 2003 (2004)

Angew. Chem. Int. Ed. 2006, 45, 7800

WO2009050290

US20090165846

US20080015355

US20010015432

US20100295032 Monomer for polymeric metal organometallic compounds

U.S. Pat. No. 7,250,226, U.S. Pat. No. 7,396,598 Pt(II) organometallic complexes, including polydentate ligands

Appl. Phys. Lett. 86, 153505 (2005)

Appl. Phys. Lett. 86, 153505 (2005)

Chem. Lett. 34, 592 (2005)

WO2002015645

US20060263635

US20060182992 US20070103060 Cu complexes

WO2009000673

US20070111026 Gold complexes

Chem. Commun. 2906 (2005) Rhenium(III) complexes

Inorg. Chem. 42, 1248 (2003) Osmium(II) complexes

U.S. Pat. No. 7,279,704 Deuterated organometallic complexes

US20030138657 Organometallic complexes with two or more metal centers

US20030152802

U.S. Pat. No. 7,090,928 Blue dopants Iridium(III) organometallic complexes

WO2002002714

WO2006009024

US20060251923 US20110057559 US20110204333

U.S. Pat. No. 7,393,599, WO2006056418, US20050260441, WO2005019373

U.S. Pat. No. 7,534,505

WO2011051404

U.S. Pat. No. 7,445,855

US20070190359, US20080297033 US20100148663

U.S. Pat. No. 7,338,722

US20020134984

Angew. Chem. Int. Ed. 47, 1 (2008)

Chem. Mater. 18, 5119 (2006)

Inorg. Chem. 46, 4308 (2007)

WO2005123873

WO2005123873

WO2007004380

WO2006082742 Osmium(II) complexes

U.S. Pat. No. 7,279,704

Organometallics 23, 3745 (2004) Gold complexes

Appl. Phys. Lett. 74, 1361 (1999) Platinum(II) complexes

WO2006098120, WO2006103874 Pt tetradentate complexes with at least one metal- carbene bond

U.S. Pat. No. 7,655,323 Exciton/hole blocking layer materials Bathocuproine compounds (e.g., BCP, BPhen)

Appl. Phys. Lett. 75, 4 (1999)

Appl. Phys. Lett. 79, 449 (2001) Metal 8-hydroxyquinolates (e.g. BAlq)

Appl. Phys. Lett. 81, 162 (2002) 5-member ring electron deficient heterocycles such as triazole, oxadiazole, imidazole, benzoimidazole

Appl. Phys. Lett. 81, 162 (2002) Triphenylene compounds

US20050025993 Fluorinated aromatic compounds

Appl. Phys. Lett. 79, 156 (2001) Phenothiazine-S-oxide

WO2008132085 Silylated five-membered nitrogen, oxygen, sulfur or phosphorus dibenzoheterocycles

WO2010079051 Aza-carbazoles

US20060121308 Electron transporting materials Anthracene- benzoimidazole compounds

WO2003060956

US20090179554 Aza triphenylene derivatives

US20090115316 Anthracene-benzothiazole compounds

Appl. Phys. Lett. 89, 063504 (2006) Metal 8-hydroxyquinolates (e.g., Alq₃, Zrq₄)

Appl. Phys. Lett. 51, 913 (1987) U.S. Pat. No. 7,230,107 Metal hydroxybenzoquinolates

Chem. Lett. 5, 905 (1993) Bathocuproine compounds such as BCP, BPhen, etc

Appl. Phys. Lett. 91, 263503 (2007)

Appl. Phys. Lett. 79, 449 (2001) 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole)

Appl. Phys. Lett. 74, 865 (1999)

Appl. Phys. Lett. 55, 1489 (1989)

Jpn. J. Apply. Phys. 32, L917 (1993) Silole compounds

Org. Electron. 4, 113 (2003) Arylborane compounds

J. Am. Chem. Soc. 120, 9714 (1998) Fluorinated aromatic compounds

J. Am. Chem. Soc. 122, 1832 (2000) Fullerene (e.g., C₆₀)

US20090101870 Triazine complexes

US20040036077 Zn (N{circumflex over ( )}N) complexes

U.S. Pat. No. 6,528,187

EXPERIMENTAL

Chemical abbreviations used throughout this document are as follows: Cy is cyclohexyl, dba is dibenzylideneacetone. EtOAc is ethyl acetate, DME is dimethoxyethane, dppe is 1,2-bis(diphenylphosphino)ethane, THF is tetrahydrofuran, DMF is dimethylformamide, DCM is dichloromethane, S-Phos is dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine, Tf is trifluoromethylsulfonate. Unless specified otherwise, references to degassing a particular solvent refer to saturating the solvent sufficiently with dry nitrogen gas (by bubbling it in the solvent) to substantially remove gaseous oxygen from the solvent.

Synthesis of Compound 113 Synthesis of N-(4-bromophenyl)-N-phenyldibenzo[b,d]thiophen-4-amine

Toluene (125 mL) was bubbled with nitrogen gas for 15 minutes, and subsequently 1,1′-Bis(diphenylphosphino)ferrocene (0.2 g, 0.4 mmol) and Pd₂(dba)₃ (0.1 g, 0.1 mmol) were added. The mixture was bubbled with nitrogen gas for 15 minutes, then N-phenyldibenzo[b,d]thiophen-4-amine (3.2 g, 11.6 mmol), 1-bromo-4-iodobenzene (4.5 g, 15.9 mmol), NaO^(t)Bu (1.5 g, 15.6 mmol) were added. The mixture was bubbled with nitrogen gas for 15 minutes and refluxed for 12 hours. After cooling, the reaction mixture was filtered through a silica pad and washed with 50% CH₂Cl₂/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 10-15% CH₂Cl₂/hexane to afford N-(4-bromophenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (4.0 g, 80% yield) as a white solid.

Synthesis of N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine

To a solution of N-(4-bromophenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (8.3 g, 19.3 mmol) in 1,4-dioxane (250 mL) was added bis(pinacolato)diboron (7.6 g, 29.9 mmol), KOAc (3.9 g, 39.8 mmol), and the solution was bubbled with nitrogen for 15 minutes. Pd(dppf)Cl₂.CH₂Cl₂ (0.5 g, 0.6 mmol) was then added to the solution, and the reaction mixture was bubbled with nitrogen for 15 minutes. The resultant mixture was refluxed for 12 hours. After cooling, H₂O (1 mL) was added and stirred for 15 min. The reaction mixture was filtered through a silica pad and washed with 75% CH₂Cl₂/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 25-40% CH₂Cl₂/hexane to afford N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine (5.9 g, 64% yield) as a white solid.

Synthesis of N-(4-(9H-carbazol-3-yl)phenyl)-N-phenyldibenzo[b,d]thiophen-4-amine

To a solution of N-phenyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]thiophen-4-amine (5.9 g, 12.4 mmol), 3-bromocarbazole (3.5 g, 14.2 mmol), K₂CO₃ (16.6 g, 120.0 mmol) in toluene (150 mL), water (50 mL) and EtOH (50 mL) was bubbled for 30 min. Pd(PPh₃)₄ (0.4 g, 0.4 mmol) was added. The mixture was bubbled for 15 min. The resultant mixture was refluxed for 12 h. After cooling, the reaction mixture was extracted by CH₂Cl₂ and dried by MgSO₄. The solvent was removed in vacuo and the residue was purified by flash chromatography using 25-50% CH₂Cl₂/hexane to afford N-(4-(9H-carbazol-3-yl)phenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (5.8 g, 91% yield) as a white solid.

Synthesis of Compound 113

Xylene (175 mL) was bubbled with nitrogen for 15 minutes, followed by addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2.3 g, 5.6 mmol) and Pd₂(dba)₃ (1.3 g, 1.4 mmol). The mixture was again bubbled nitrogen for 15 minutes, then N-(4-(9H-carbazol-3-yl)phenyl)-N-phenyldibenzo[b,d]thiophen-4-amine (3.4 g, 6.6 mmol), 4-iododibenzothiophene (3.3 g, 10.6 mmol), sodium tert-butoxide (1.4 g, 14.0 mmol) were added. The mixture was bubbled with nitrogen for 15 minutes and refluxed for 12 hours. After cooling, the reaction mixture was filtered through a silica pad and washed with 80% CH₂Cl₂/hexane. The solvent was removed in vacuo and the residue was purified by flash chromatography using 20-35% CH₂Cl₂/hexane to afford Compound 113 (2.9 g, 63% yield) as a white solid.

Synthesis of Compound 178 Synthesis of bis(4-bromophenyl)amine

N-bromosuccinimide (17.8 g, 0.1 mol) in 50 mL of DMF was added slowly to diphenylamine (8.46 g, 0.05 mol) in 50 mL of DMF at 0° C. in 30 minutes. The reaction was allowed to warm to room temperature and stir overnight. The white precipitate was filtered and air dried, and 16 g of product was collected.

Synthesis of di([1,1′-biphenyl]-4-yl)amine

Bis(4-bromophenyl)amine (4.0 g, 12.3 mmol) and phenylboronic acid (4.0 g, 32.7 mmol) were mixed in 250 mL of toluene and 60 mL of ethanol. The solution was bubbled with nitrogen while stirring for 15 minutes. Pd(PPh₃)₄ (1.4 g, 1.23 mmol) and K₃PO₄ (13.5 g, 64 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through filter paper and the solvent was then evaporated. The solid was redissolved in nitrogen-purged hot toluene and was filtered through a Celite®/silica pad when the solution was still hot. The solvent was then evaporated. The white crystalline solid was washed by hexane and air dried to obtain 3.8 g of product.

Synthesis of N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1′-biphenyl]-4-amine

Di([1,1′-biphenyl]-4-yl)amine (3.5 g, 10.9 mmol) and 1-bromo-4-iodobenzene (6.0 g, 21.3 mmol) were mixed in 300 mL of dry toluene. The solution was bubbled with nitrogen while stirring for 15 minutes. Pd(OAc)₂ (36 mg, 0.16 mmol), triphenylphosphine (0.16 g, 0.6 mmol) and sodium t-butoxide (2.0 g, 20.8 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 3.9 g of product.

Synthesis of 9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole

Carbazole (0.62 g, 3.67 mmol) and 4-iododibenzothiophene (1.2 g, 3.87 mmol) were mixed in 70 mL of dry xylene. The solution was bubbled nitrogen while stirring for 15 minutes. Pd₂(dba)₃ (0.16 g, 0.17 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.24 g, 0.58 mmol) and sodium tert-butoxide (1.0 g, 10.4 mmol) were added in sequence. The mixture was heated to reflux for 3 days under nitrogen. After cooling, the reaction mixture was filtered through a Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 0.64 g of product.

Synthesis of 3-bromo-9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole

N-bromosuccinimide (0.31 g, 1.74 mmol) in 5 mL DMF was added slowly to 9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole (0.6 g, 1.72 mmol) in 50 mL of DCM at 0° C. The reaction was allowed to warm to room temp and stirred overnight. The reaction mixture was extracted with DCM and dried over MgSO₄ and the solvent was evaporated. The residue was purified by column chromatography using DCM:hexane (1:4, v/v) as the eluent to obtain 0.45 g of product.

Synthesis of 9-(dibenzo[b,d]thiophen-4-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

3-bromo-9-(dibenzo[b,d]thiophen-4-yl)-9H-carbazole (0.45 g, 1.1 mmol), bis(pinacolato)diboron (0.43 g, 1.4 mmol) and KOAc (0.31 g, 3.1 mmol) were mixed in 150 mL of dry 1,4-dioxane. The solution was bubbled with nitrogen while stirring for 15 minutes, then Pd(dppf)Cl₂.CH₂Cl₂ (26 mg, 0.03 mmol) was added. The mixture was heated to reflux overnight under nitrogen. After cooling, the reaction mixture was filtered through Celite®/silica pad and the solvent was then evaporated. The residue was then purified by column chromatography using DCM:hexane (3:7, v/v) as the eluent to obtain 0.4 g of product.

Synthesis of Compound 178

N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1′-biphenyl]-4-amine (2.5 g, 5.25 mmol), and 9-(dibenzo[b,d]thiophen-4-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (2.64 g, 5.58 mmol) were mixed in 250 mL of toluene and 30 mL of deionized water. The solution was bubbled with nitrogen while stirring for 15 minutes, then Pd₂(dba)₃ (0.12 g, 0.13 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.21 g, 0.51 mmol) and K₃PO₄ (3.5 g, 16.5 mmol) were added in sequence. The mixture was heated to reflux overnight under nitrogen. Bromobenzene (1 mL) was added to the reaction mixture and the reaction was further refluxed for 4 hours. After cooling, the reaction mixture was filtered through a Celite®/silica pad and the solvent was then evaporated. Compound 178 (2.4 g) was collected and purified by recrystallization from 20 mL of degassed toluene.

Compound 182 Synthesis of 9-(triphenylen-2-yl)-9H-carbazole

To a stirred solution of Pd₂(dba)₃ (0.52 g, 0.57 mmol) in o-xylene (140 mL), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.94 g, 2.3 mmol) was added and degassed with nitrogen for 15 minutes. Carbazole (5.33 g, 31.9 mmol) and 2-bromotriphenylene (7.0 g, 22.7 mmol), sodium tert-butoxide (6.57 g, 68.3 mmol) were added and degassed with nitrogen for another 15 minutes. The reaction was refluxed for 2 days. The reaction mixture was filtered through silica, washed with DCM and dried under vacuum. Silica gel chromatography with 10% DCM/hexane, yielded 4.98 g of a while solid (56%) as the product.

Synthesis of 3-bromo-9-(triphenylen-2-yl)-9H-carbazole

To a stirred solution of 9-(triphenylen-2-yl)-9H-carbazole (4.7 g, 11.9 mmol) in DMF (24 mL) at 0° C. under N₂, NBS (N-bromosuccinimide) (2.1 g, 11.9 mmol) in DMF (24 mL) was added dropwise. After the completion of addition, the reaction mixture was warmed to room temperature overnight with vigorous stirring. The reaction mixture was precipitated with water and the solid was filtered. The pale grey solid was re-dissolved in a small amount of THF, added on a silica plug and flushed with 30% DCM/hexane. The filtrate was dried under vacuum and the white solid was used without further purification (5.5 g, 98%).

Synthesis of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(triphenylen-2-yl)-9H-carbazole

To a stirred solution of 3-bromo-9-(triphenylen-2-yl)-9H-carbazole (3.0 g, 6.4 mmol) in 1,4-dioxane (90 mL), bis(pinacolato)diboron (2.4 g, 9.5 mmol) and KOAc (1.8 g, 19.1 mmol) were added and degassed with nitrogen for 15 min, then Pd(dppf)Cl₂.CH₂Cl₂ (0.14 g, 0.2 mmol) was added and the mixture was degassed with nitrogen for another 15 minutes. The solution was refluxed for 2 days. After cooling to room temperature, water (1 mL) was added and the reaction mixture was stirred for 30 minutes. The reaction mixture was filtered through silica and dried under vacuum. The solid was column chromatographed with 20-50% DCM/hexane, yielding 2.0 g of a while solid (61%) as the product.

Synthesis of Compound 182

To a stirred solution of N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-[1,1′-biphenyl]-4-amine (0.9 g, 1.9 mmol) in toluene (29 mL) and water (2.9 mL), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(triphenylen-2-yl)-9H-carbazole (1.0 g, 1.9 mmol) and K₃PO₄ (2.4 g, 11.3 mmol) were added and the mixture was degassed with nitrogen for 15 minutes, then Pd₂(dba)₃ (86 mg, 0.09 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.16 g, 0.38 mmol) were added and degassed with nitrogen for another 15 minutes. The mixture was refluxed overnight. After cooling to room temperature, the reaction mixture was filtered through silica, washed with DCM and dried under vacuum. It was column chromatographed with 20-50% DCM/hexane yielding 1.03 g of a while solid (69%) as Compound 182.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

What is claimed is:
 1. A compound having the formula:

wherein Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl; and wherein X is selected from the group consisting of O, S, and Se; wherein R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution; and wherein R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 2. The compound of claim 1, wherein R₃ and R₄ are independently selected from the group consisting of alkyl, heteroalkyl, arylalkyl, aryl, and heteroaryl.
 3. The compound of claim 1, wherein R₃ and R₄ are hydrogen or deuterium.
 4. The compound of claim 1, wherein the compound has the formula:


5. The compound of claim 1, wherein X is O or S.
 6. The compound of claim 1, wherein Ar₁ and Ar₂ are aryl.
 7. A first device comprising an organic light emitting device, further comprising: an anode; a cathode; an emissive layer disposed between the anode and the cathode; a hole injection layer disposed between the anode and the emissive layer; a first hole transport layer disposed between the hole injection layer and the emissive layer; and a second hole transport layer disposed between the first hole transport layer and the emissive layer; and wherein the second hole transport layer comprises a compound of formula:

wherein Ar₁, Ar₂, and Ar₅ are independently selected from the group consisting of aryl and heteroaryl; and wherein R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 8. The first device of claim 7, wherein the compound has the formula:

wherein X is selected from the group consisting of O, S, and Se; wherein R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution; and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 9. The first device of claim 7, wherein the second hole transport layer is disposed adjacent to the first hole transport layer.
 10. The first device of claim 7, wherein the first hole transport layer is thicker than the second hole transport layer.
 11. The first device of claim 7, wherein the first hole transport layer comprises a compound with the formula:

wherein Ar_(a), Ar_(b), Ar_(c) and Ar_(d) are independently selected from the group consisting of aryl and heteroaryl.
 12. The first device of claim 7, wherein the triplet energy of the compound of Formula II is higher than the emission energy of the emissive layer.
 13. The first device of claim 7, further comprising a first dopant material that is an emissive dopant comprising a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:

wherein R_(a), R_(b), R_(c), and R_(d) may represent mono, di, tri, or tetra substitution, or no substitution; wherein R_(a), R_(b), R_(c), and R_(d) are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) are optionally joined to form a fused ring or form a multidentate ligand.
 14. The first device of claim 7, wherein the first device is a consumer product.
 15. The first device of claim 7, wherein the first device is an organic light-emitting device.
 16. The first device of claim 7, wherein the first device comprises a lighting panel.
 17. A first device comprising an organic light emitting device, further comprising: an anode; a cathode; a first organic layer disposed between the anode and the cathode; and wherein the first organic layer comprises a compound of formula:

wherein Ar₁ and Ar₂ are independently selected from the group consisting of aryl and heteroaryl; and wherein X is selected from the group consisting of O, S, and Se; wherein R₁ and R₂ independently represent mono, di, tri, tetra substitution, or no substitution; and wherein R₁, R₂, R₃ and R₄ are independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
 18. The first device of claim 17, wherein the first organic layer is an emissive layer.
 19. The first device of claim 18, wherein the emissive layer is a phosphorescent emissive layer. 